Well-defined structurally organised porphyrin triads of a controlled geometry and nanoscale size have been formed in liquid solutions using the combination of a covalent approach and non-covalent self-assembly. The triads contain zinc-octaethylporphyrin chemical dimer, (ZnOEP) 2 Ph, with covalently linked electron acceptors (p-benzoquinone, Q or pyromellitimide, Pim), and additional dipyridyl-substituted tetrapyrrole extra-ligands. Steady-state, picosecond fluorescence (Δt 1 / 2 ~75ps) and femtosecond pump-probe (Δ 1 / 2 ~280fs) data show that non-radiative deactivation of the dimer S 1 -states (τ S <1ps) is due to both the S-S energy transfer (ZnOEP) 2 Ph->extra-ligand and the sequential photoinduced electron transfer (ZnOEP) 2 Ph->Q (or Pim) at r D A =10.8Å. The additional decay shortening of the extra-ligand S 1 -states by 3-6 times (toluene, 293K) is attributed to the increased ''superexchange'' mediated long distant (r D A ~18-21Å) one-step electron transfer extra-ligand->Q (or Pim).